Multi-stage process and device for treatment heavy marine fuel oil and resultant composition and the removal of detrimental solids

ABSTRACT

A multi-stage process for reducing the environmental contaminants in an ISO8217 compliant Feedstock Heavy Marine Fuel Oil involving a core desulfurizing process and a Detrimental Solids removal unit as either a pre-treating step or post-treating step to the core process. The Product Heavy Marine Fuel Oil complies with ISO 8217 for residual marine fuel oils and has a sulfur level has a maximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.05 mass % to 1.0 mass and a Detrimental Solids content less than 60 mg/kg. A process plant for conducting the process is also disclosed.

BACKGROUND

There are two basic marine fuel types, distillate based marine fuel, andresidual based marine fuel. Distillate based marine fuel, also known asMarine Gas Oil (MGO) or Marine Diesel Oil (MDO) comprises petroleumfractions separated from crude oil in a refinery via a distillationprocess. Gasoil (also known as medium diesel) is a petroleum distillateintermediate in boiling range and viscosity between kerosene andlubricating oil containing a mixture of C10-C19 hydrocarbons. Gasoil isused to heat homes and is used for heavy equipment such as cranes,bulldozers, generators, bobcats, tractors and combine harvesters.Generally maximizing gasoil recovery from residues is the most economicuse because a refinery can crack gas oils into valuable gasoline anddistillates. Diesel oils are similar to gas oils with diesel containinga mixture of C10 through C19 hydrocarbons, which include approximately60% or more aliphatic hydrocarbons, 1-2% olefinic hydrocarbons, and 35%or less aromatic hydrocarbons. Marine Diesels may contain no over 15%residual process streams, and optionally no over 5% volume of polycyclicaromatic hydrocarbons (asphaltenes). Diesel fuels are primarily utilizedas a land transport fuel and as blending component with kerosene to formaviation jet fuel.

Residual based fuels or Heavy Marine Fuel Oil (HMFO) comprises a mixtureof process residues—the fractions that don't boil or vaporize even undervacuum conditions, and have an asphaltenes content between 3 and 20percent by weight. Asphaltenes are large and complex polycyclichydrocarbons that contribute to the fuel density, SARA properties andlubricity properties of HMFO which are desirable. Asphaltenes, however,have a propensity to form complex and waxy precipitates, especially inthe presence of aliphatic (paraffinic) hydrocarbons. Once asphalteneshave precipitated out, they are notoriously difficult to re-dissolve andare described as fuel tank sludge in the marine shipping industry andmarine bunker fueling industry.

Large ocean-going ships have relied upon HMFO to power large two strokediesel engines for over 50 years. HMFO is a blend of polycyclicaromatics and residual hydrocarbons generated in the crude oil refineryprocess. Typical streams included in the formulation of HMFO include,but are not limited to: atmospheric tower bottoms (i.e. atmosphericresidues), vacuum tower bottoms (i.e. vacuum residues) visbreakerresidue, FCC Light Cycle Oil (LCO), FCC Heavy Cycle Oil (HCO) also knownas FCC bottoms, FCC Slurry Oil, heavy gas oils; delayed cracker oil(DCO), polycylic aromatic hydrocarbons, De-asphalted oil (DAO);reclaimed land transport motor oils; slop oils, and minor portions (lessthan 20% vol.) of cutter oil, kerosene or diesel to achieve a desiredviscosity. HMFO has an aromatic content higher than the marinedistillate fuels noted above. The HMFO composition is complex and varieswith the source of crude oil processed by the refinery and the processesutilized within the refinery to extract the most value out of a barrelof crude oil. The mixture of components is generally characterized asbeing viscous, high in sulfur and metal content, and high in asphaltenesmaking HMFO the one product of the refining process that has a perbarrel value less than the feedstock crude oil itself.

Industry statistics indicate that about 90% of the HMFO sold contains3.5 weight % sulfur. With an estimated total worldwide consumption ofHMFO of approximately 300 million tons per year, the annual productionof sulfur dioxide by the shipping industry is estimated to be over 21million tons per year. Emissions from HMFO burning in ships contributesignificantly to both global air pollution and local air pollutionlevels.

MARPOL, the International Convention for the Prevention of Pollutionfrom Ships, as administered by the International Maritime Organization(IMO) was enacted to prevent pollution from ships. In 1997, a new annexwas added to MARPOL; the Regulations for the Prevention of Air Pollutionfrom Ships—Annex VI to minimize airborne emissions from ships and theircontribution to air pollution. A revised Annex VI with tightenedemissions limits on sulfur oxides, nitrogen oxides, ozone depletingsubstances and volatile organic compounds (SOx, NOx, ODS, VOC) wasadopted in October 2008 and effective 1 Jul. 2010 (hereafter calledAnnex VI (revised)).

MARPOL Annex VI (revised) established a set of stringent emissionslimits for vessel operations in designated Emission Control Areas(ECAs). The ECAs under MARPOL Annex VI (revised) are: i) Baltic Seaarea—as defined in Annex I of MARPOL—SOx only; ii) North Sea area—asdefined in Annex V of MARPOL—SOx only; iii) North American—as defined inAppendix VII of Annex VI of MARPOL—SOx, NOx and PM; and, iv) UnitedStates Caribbean Sea area—as defined in Appendix VII of Annex VI ofMARPOL—SOx, NOx and PM.

Annex VI (revised) was codified in the United States by the Act toPrevent Pollution from Ships (APPS). Under the authority of APPS, theU.S. Environmental Protection Agency (the EPA), in consultation with theUnited States Coast Guard (USCG), promulgated regulations whichincorporate by reference the full text of MARPOL Annex VI (revised). See40 C.F.R. § 1043.100(a)(1). On Aug. 1, 2012 the maximum sulfur contentof all marine fuel oils used onboard ships operating in US waters/ECAcannot exceed 1.00% wt. (10,000 ppm) and on Jan. 1, 2015 the maximumsulfur content of all marine fuel oils used in the North American ECAwas lowered to 0.10% wt. (1,000 ppm). At the time of implementation, theUnited States government indicated that vessel operators must vigorouslyprepare for the 0.10% wt. (1,000 ppm) US ECA marine fuel oil sulfurstandard. To encourage compliance, the EPA and USCG refused to considerthe cost of compliant low sulfur fuel oil to be a valid basis forclaiming that compliant fuel oil was not available for purchase. For thepast five years there has been a very strong economic incentive to meetthe marine industry demands for low sulfur HMFO, however technicallyviable solutions have not been realized. There has been an on-going andurgent demand for processes and methods for making a low sulfur HMFOcompliant with ECA MARPOL Annex VI emissions requirements.

Under the revised MARPOL Annex VI, a global sulfur cap for HMFO (theprimary source for Sox emissions from ships) was set at 3.50% wt.effective 1 Jan. 2012; then further reduced to 0.50% wt, effective 1Jan. 2020. Under the global limit, all ships must use HMFO with a sulfurcontent of not over 0.50% wt. This regulation has been the subject ofmuch discussion in both the marine shipping and marine fuel bunkeringindustry. There has been a very strong economic incentive to meet theinternational marine industry demands for low sulfur HMFO that is ISO8217 compliant, however technically viable solutions have not beenrealized. There is an on-going and urgent demand for processes andmethods for making a low sulfur HMFO ISO 8217 compliant with the globalMARPOL Annex VI emissions requirements.

Primary Control Solutions:

A focus for compliance with the MARPOL requirements has been on primarycontrol solutions for reducing the sulfur levels in marine fuelcomponents prior to combustion based on the substitution of HMFO withalternative fuels. Because of the potential risks to ships propulsionsystems (i.e. fuel systems, engines, etc.) when a ship switches fuel,the conversion process must be done safely and effectively to avoid anytechnical issues. However, each alternative fuel has both economic andtechnical difficulties adapting to the decades of shippinginfrastructure and bunkering systems based upon HMFO utilized by themarine shipping industry.

Replacement of Heavy Fuel Oil with Marine Gas Oil or Marine Diesel:

A third proposed primary solution is to simply replace HMFO with marinegas oil (MGO) or marine diesel (MDO). The first major difficulty is theconstraint in global supply of distillate materials that make up over90% vol of MGO and MDO. It is reported that the effective spare capacityto produce MGO is less than 100 million metric tons per year resultingin an annual shortfall in marine fuel of over 200 million metric tonsper year. Refiners not only lack the capacity to increase the productionof MGO, but they have no economic motivation because higher value andhigher margins can be obtained from ultra-low sulfur diesel fuel forland-based transportation systems (i.e. trucks, trains, mass transitsystems, heavy construction equipment, etc.). A distillate only solutionalso ignores the economic impacts of disposing of the refinery streamsthat previously went to the high sulfur HMFO blending pool.

Blending:

Another primary solution is the blending of HMFO with lower sulfurcontaining fuels such as low sulfur marine diesel (0.1% wt. sulfur) toachieve a Product HMFO with a sulfur content of 0.5% wt. In atheoretical straight blending approach (based on linear blending) every1 ton of HSFO (3.5% sulfur) requires 7.5 tons of MGO or MDO materialwith 0.1% wt. S to achieve a sulfur level of 0.5% wt. HMFO. One of skillin the art of fuel blending will immediately understand that blendinglarge volumes of distillate into high sulfur HMFO hurts key propertiesof the HMFO, specifically lubricity, viscosity and density aresubstantially altered. Further a blending process may create a fuel thatis unstable and incompatible with other blends of distillate and HMFO. Ablended fuel is likely to result in the precipitation of asphaltenesand/or waxing out of highly paraffinic materials from the distillatematerial forming an intractable fuel tank sludge. Such a risk to theprimary propulsion system is not acceptable for a cargo ship in the openocean.

Processing of Residual Oils.

For the past several decades, the focus of refining industry researchefforts related to the processing of heavy oils (crude oils, distressedoils, or residual oils) has been on upgrading the properties of theselow value refinery process oils to create lighter oils with greatervalue. The challenge has been that crude oil, distressed oil andresidues can be unstable and contain high levels of sulfur, nitrogen,phosphorous, metals (especially vanadium and nickel) and asphaltenes.Much of the nickel and vanadium is in difficult to remove chelates withporphyrins. Vanadium and nickel porphyrins and other metal organiccompounds are responsible for catalyst contamination and corrosionproblems in the refinery. The sulfur, nitrogen, and phosphorous, areremoved because they are well-known poisons for the precious metal(platinum and palladium) catalysts utilized in the processes downstreamof the atmospheric or vacuum distillation towers.

The difficulties treating atmospheric or vacuum residual streams hasbeen known for many years and has been the subject of considerableresearch and investigation. Numerous residue-oil conversion processeshave been developed in which the goals are same, 1) create a morevaluable, preferably distillate range hydrocarbon product; and 2)concentrate the contaminates such as sulfur, nitrogen, phosphorous,metals and asphaltenes into a form (coke, heavy coker residue, FCCslurry oil) for removal from the refinery stream. Well known andaccepted practice in the refining industry is to increase the reactionseverity (elevated temperature and pressure) to produce hydrocarbonproducts that are lighter and more purified, increase catalyst lifetimes and remove sulfur, nitrogen, phosphorous, metals and asphaltenesfrom the refinery stream.

In summary, since the announcement of the MARPOL standards reducing theglobal levels of sulfur in HMFO, refiners of crude oil have beenunsuccessful in their technical efforts to create a process for theproduction of a low sulfur substitute for HMFO. Despite the stronggovernmental and economic incentives and needs of the internationalmarine shipping industry, refiners have little economic reason toaddress the removal of environmental contaminates from HMFOs. The globalrefining industry has been focused upon generating greater value fromeach barrel of oil by creating light hydrocarbons (i.e. diesel andgasoline) and concentrating the environmental contaminates intoincreasingly lower value streams (i.e. residues) and products (petroleumcoke, HMFO). Shipping companies have focused on short term solutions,such as the installation of scrubbing units, or adopting the limited useof more expensive low sulfur marine diesel and marine gas oils as asubstitute for HMFO. On the open seas, most if not all major shippingcompanies continue to utilize the most economically viable fuel, that isHMFO. There remains a long standing and unmet need for processes anddevices that remove the environmental contaminants (i.e. sulfur,nitrogen, phosphorous, metals especially vanadium and nickel) from HMFOwithout altering the qualities and properties that make HMFO the mosteconomic and practical means of powering ocean going vessels.

SUMMARY

It is a general objective to reduce the environmental contaminates andDetrimental Solids from a Heavy Marine Fuel Oil (HMFO) in a multi stageprocess that minimizes the changes in the desirable properties of theHMFO and minimizes the unnecessary production of by-product hydrocarbons(i.e. light hydrocarbons having C1-C4 and wild naphtha (C5-C20)).

A first aspect and illustrative embodiment encompasses a multi-stageprocess for reducing the environmental contaminants and DetrimentalSolids in a Feedstock Heavy Marine Fuel Oil, the process involving:contacting a Feedstock Heavy Marine Fuel Oil with a Detrimental SolidsRemoval Unit (DSRU) to give a pre-treated Feedstock Heavy Marine FuelOil; mixing a quantity of the pre-treated Feedstock Heavy Marine FuelOil with a quantity of Activating Gas mixture to give a FeedstockMixture; contacting the Feedstock Mixture with one or more catalystsunder desulfurizing conditions to form a Process Mixture from theFeedstock Mixture; receiving the Process Mixture and separating theProduct Heavy Marine Fuel Oil liquid components of the Process Mixturefrom the gaseous components and by-product hydrocarbon components of theProcess Mixture and, discharging the Product Heavy Marine Fuel Oil.

A second aspect and illustrative embodiment encompasses a device forreducing environmental contaminants and Detrimental Solids in aFeedstock HMFO and producing a Product HMFO. The illustrative devicesembody the above illustrative processes on a commercial scale.

A third aspect and illustrative embodiment encompasses a Heavy MarineFuel Oil composition resulting from the above illustrative processes.

DESCRIPTION OF DRAWINGS

FIG. 1 is a process block flow diagram of an illustrative core processto produce Product HMFO.

FIG. 2 is a process flow diagram of a multistage process utilizing aDetrimental Solids removal unit to pre-treat the feedstock HMFO and asubsequent core process to produce Product HMFO.

FIG. 3 is a diagram illustrating the details of a Detrimental Solidsremoval unit

FIG. 4 is a basic schematic diagram of a plant to produce Product HMFOutilizing a combination of a Detrimental Solids removal unit topre-treat the feedstock HMFO and a subsequent core process to produceProduct HMFO.

FIG. 5 is a basic schematic diagram of a plant to produce Product HMFOutilizing a combination of a Core Process and a subsequent DetrimentalSolids Removal Unit to produce Product HMFO.

DETAILED DESCRIPTION

The inventive concepts as described herein utilize terms that should bewell known to one of skill in the art, however certain terms areutilized having a specific intended meaning and these terms are definedbelow:

Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant withthe ISO 8217 (2017) standards for the bulk properties of residual marinefuels except for the concentration levels of the EnvironmentalContaminates.

Detrimental Solids are suspended solid particulate materials present inthe HMFO having a diameter in the range of 1000 microns to 0.1 microns.

Environmental Contaminates are organic and inorganic components of HMFOthat result in the formation of SO_(x), NO_(x) and particulate materialsupon combustion.

Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the bulk properties of residual marine fuels exceptfor the concentration of Environmental Contaminates, preferably theFeedstock HMFO has a sulfur content greater than the global MARPOLstandard of 0.5% wt. sulfur, and preferably and has a sulfur content(ISO 14596 or ISO 8754) between the range of 5.0% wt. to 1.0% wt.

Product HMFO is a petroleum product fuel compliant with the ISO 8217(2017) standards for the bulk properties of residual marine fuels andachieves a sulfur content lower than the global MARPOL standard of 0.5%wt. sulfur (ISO 14596 or ISO 8754), and preferably a maximum sulfurcontent (ISO 14596 or ISO 8754) between the range of 0.05% wt. to 1.0%wt.

Activating Gas: is a mixture of gases utilized in the process combinedwith the catalyst to remove the environmental contaminates from theFeedstock HMFO.

Fluid communication: is the capability to transfer fluids (eitherliquid, gas or combinations thereof, which might have suspended solids)from a first vessel or location to a second vessel or location, this mayencompass connections made by pipes (also called a line), spools,valves, intermediate holding tanks or surge tanks (also called a drum).

Merchantable quality: is a level of quality for a residual marine fueloil so the fuel is fit for the ordinary purpose it should serve (i.e.serve as a residual fuel source for a marine ship) and can becommercially sold as and is fungible with heavy or residual marinebunker fuel.

Bbl or bbl: is a standard volumetric measure for oil; 1 bbl=0.1589873m³; or 1 bbl=158.9873 liters; or 1 bbl=42.00 US liquid gallons.

Bpd: is an abbreviation for Bbl per day.

SCF: is an abbreviation for standard cubic foot of a gas; a standardcubic foot (at 14.73 psi and 60° F.) equals 0.0283058557 standard cubicmeters (at 101.325 kPa and 15° C.).

The inventive concepts are illustrated in more detail in thisdescription referring to the drawings, in which FIG. 1 shows thegeneralized block process flows for a core process of reducing theenvironmental contaminates in a Feedstock HMFO and producing a ProductHMFO. A predetermined volume of Feedstock HMFO (2) is mixed with apredetermined quantity of Activating Gas (4) to give a FeedstockMixture. The Feedstock HMFO utilized generally complies with the bulkphysical and certain key chemical properties for a residual marine fueloil otherwise compliant with ISO 8217 (2017) exclusive of theEnvironmental Contaminates. More particularly, when the EnvironmentalContaminate is sulfur, the concentration of sulfur in the Feedstock HMFOmay be between the range of 5.0% wt. to 1.0% wt. The Feedstock HMFOshould have bulk physical properties required of an ISO 8217 (2017)compliant HMFO. This includes having bulk properties of: a kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a density at 15° C. (ISO 3675) between the range of 991.0 kg/m³to 1010.0 kg/m³; a CCAI in the range of 780 to 870; a flash point (ISO2719) no lower than 60° C. Properties of the Feedstock HMFO connected tothe formation of particulate material (PM) include: a maximum totalsediment—aged (ISO 10307-2) of less than 0.10% wt. and a maximum carbonresidue—micro method (ISO 10370) less than 20% wt. and preferably lessthan 18% wt and an aluminum plus silicon (ISO 10478) content less than60 mg/kg. Environmental Contaminates other than sulfur that may bepresent in the Feedstock HMFO over the ISO requirements may includevanadium, nickel, iron, aluminum and silicon substantially reduced bythe process of the present invention. However, one of skill in the artwill appreciate that the vanadium content serves as a general indicatorof these other Environmental Contaminates. In one preferred embodimentthe vanadium content is ISO compliant so the Feedstock MHFO has avanadium content (ISO 14597) between the range from 350 mg/kg to 450 ppmmg/kg.

As for the properties of the Activating Gas, the Activating Gas shouldbe selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane. The mixture of gases within the Activating Gasshould have an ideal gas partial pressure of hydrogen (p_(H2)) greaterthan 80% of the total pressure of the Activating Gas mixture (P) andmore preferably wherein the Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 90% of the total pressure ofthe Activating Gas mixture (P). It will be appreciated by one of skillin the art that the molar content of the Activating Gas is anothercriteria the Activating Gas should have a hydrogen mole fraction in therange between 80% and 100% of the total moles of Activating Gas mixture.

The Feedstock Mixture (i.e. mixture of Feedstock HMFO and ActivatingGas) is brought up to the process conditions of temperature and pressureand introduced into a first vessel, preferably a reactor vessel, so theFeedstock Mixture is then contacted with one or more catalysts (8) toform a Process Mixture from the Feedstock Mixture.

The core process reactive conditions are selected so the ratio of thequantity of the Activating Gas to the quantity of Feedstock HMFO is 250scf gas/bbl of Feedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO;and preferably between 2000 scf gas/bbl of Feedstock HMFO 1 to 5000 scfgas/bbl of Feedstock HMFO more preferably between 2500 scf gas/bbl ofFeedstock HMFO to 4500 scf gas/bbl of Feedstock HMFO. The processconditions are selected so the total pressure in the first vessel isbetween of 250 psig and 3000 psig; preferably between 1000 psig and 2500psig, and more preferably between 1500 psig and 2200 psig. The processreactive conditions are selected so the indicated temperature within thefirst vessel is between of 500° F. to 900° F., preferably between 650°F. and 850° F. and more preferably between 680° F. and 800° F. Theprocess conditions are selected so the liquid hourly space velocitywithin the first vessel is between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³ catalyst and0.5 oil/hour/m³ catalyst; and more preferably between 0.1 oil/hour/m³catalyst and 0.3 oil/hour/m³ catalyst to achieve deep desulfurizationwith product sulfur levels below 0.1 ppmw.

One of skill in the art will appreciate that the core process reactiveconditions are determined to consider the hydraulic capacity of theunit. Exemplary hydraulic capacity for the treatment unit may be between100 bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day.

The core process may utilize one or more catalyst systems selected fromthe group consisting of: an ebulliated bed supported transition metalheterogeneous catalyst, a fixed bed supported transition metalheterogeneous catalyst, and a combination of ebulliated bed supportedtransition metal heterogeneous catalysts and fixed bed supportedtransition metal heterogeneous catalysts. One of skill in the art willappreciate that a fixed bed supported transition metal heterogeneouscatalyst will be the technically easiest to implement and is preferred.The transition metal heterogeneous catalyst comprises a porous inorganicoxide catalyst carrier and a transition metal catalyst. The porousinorganic oxide catalyst carrier is at least one carrier selected fromthe group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier. The transition metal component of thecatalyst is one or more metals selected from the group consisting ofgroup 6, 8, 9 and 10 of the Periodic Table. In a preferred andillustrative embodiment, the transition metal heterogeneous catalyst isa porous inorganic oxide catalyst carrier and a transition metalcatalyst, in which the preferred porous inorganic oxide catalyst carrieris alumina and the preferred transition metal catalyst is Ni—Mo, Co—Mo,Ni—W or Ni—Co—Mo.

The Process Mixture (10) in this core process is removed from the firstvessel (8) and from being in contact with the one or more catalystmaterials and is sent via fluid communication to a second vessel (12),preferably a gas-liquid separator or hot separators and cold separators,for separating the liquid components (14) of the Process Mixture fromthe bulk gaseous components (16) of the Process Mixture. The gaseouscomponents (16) are treated beyond the battery limits of the immediateprocess. Such gaseous components may include a mixture of Activating Gascomponents and lighter hydrocarbons (mostly methane, ethane and propanebut some wild naphtha) that may have been formed as part of theby-product hydrocarbons from the process.

The Liquid Components (16) in this core process are sent via fluidcommunication to a third vessel (18), preferably a fuel oil productstripper system, for separating any residual gaseous components (20) andby-product hydrocarbon components (22) from the Product HMFO (24). Theresidual gaseous components (20) may be a mixture of gases selected fromthe group consisting of: nitrogen, hydrogen, carbon dioxide, hydrogensulfide, gaseous water, C1-C5 hydrocarbons. This residual gas is treatedoutside of the battery limits of the immediate process, combined withother gaseous components (16) removed from the Process Mixture (10) inthe second vessel (12). The liquid by-product hydrocarbon component,which are condensable hydrocarbons formed in the process (22) may be amixture selected from the group consisting of C4-C20 hydrocarbons (wildnaphtha) (naphtha—diesel) and other condensable light liquid (C4-C8)hydrocarbons that can be utilized as part of the motor fuel blendingpool or sold as gasoline and diesel blending components on the openmarket. These liquid by-product hydrocarbons should be less than 15% wt,preferably less than 5% wt. and more preferably less than 3% wt. of theoverall process mass balance.

The Product HMFO (24) resulting from the core process is discharged viafluid communication into storage tanks beyond the battery limits of theimmediate process. The Product HMFO complies with ISO 8217 (2017) andhas a sulfur content (ISO 14596 or ISO 8754) between the range of 0.05mass % to 1.0 mass % preferably a sulfur content (ISO 14596 or ISO 8754)between the range of 0.05 mass % ppm and 0.7 mass % and more preferablya sulfur content (ISO 14596 or ISO 8754) between the range of 0.1 mass %and 0.5 mass %. The vanadium content of the Product HMFO is also ISOcompliant with a maximum vanadium content (ISO 14597) between the rangefrom 350 mg/kg to 450 ppm mg/kg, preferably a vanadium content (ISO14597) between the range of 200 mg/kg and 300 mg/kg and more preferablya vanadium content (ISO 14597) less than 50 mg/kg.

The Product HFMO should have bulk physical properties that are ISOcompliant of: a kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI in the range of780 to 870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) of less than 0.10% wt.; a carbonresidue—micro method (ISO 10370) less than 20.00% wt. The Product HMFOwill have a sulfur content (ISO 14596 or ISO 8754) between 1% and 20% ofthe maximum sulfur content of the Feedstock Heavy Marine Fuel Oil. Thatis the sulfur content of the Product will be reduced by about 80% orgreater when compared to the Feedstock HMFO. Similarly, the vanadiumcontent (ISO 14597) of the Product Heavy Marine Fuel Oil is between 1%and 20% of the maximum vanadium content of the Feedstock Heavy MarineFuel Oil. One of skill in the art will appreciate that the above dataindicates a substantial reduction in sulfur and vanadium contentindicate a process having achieved a substantial reduction in theEnvironmental Contaminates from the Feedstock HMFO while maintaining thedesirable properties of an ISO 8217 compliant HMFO.

As a side note, the residual gaseous component is a mixture of gasesselected from the group consisting of: nitrogen, hydrogen, carbondioxide, hydrogen sulfide, gaseous water, C1-C5 hydrocarbons. An aminescrubber will effectively remove the hydrogen sulfide content which canthen be processed using technologies and processes well known to one ofskill in the art. In one preferable illustrative embodiment, thehydrogen sulfide is converted into elemental sulfur using the well-knownClaus process. An alternative embodiment utilizes a proprietary processfor conversion of the Hydrogen sulfide to hydrosulfuric acid. Eitherway, the sulfur is removed from entering the environment prior tocombusting the HMFO in a ships engine. The cleaned gas can be vented,flared or more preferably recycled back for use as Activating Gas.

Detrimental Solids Removal Process:

It will be appreciated by one of skill in the art, that the conditionsutilized in the core process have been intentionally selected tominimize cracking of hydrocarbons, but remove significant levels ofsulfur from the Feedstock HMFO. However, one of skill in the art willalso appreciate there may be certain Detrimental Solids present in theFeedstock HMFO removal of which would have a positive impact upon thedesirable bulk properties of the Product HMFO. These processes andsystems must achieve this without substantially altering the desirablebulk properties (i.e. compliance with ISO 8217 (2017) exclusive ofsulfur content) of the Product HMFO.

The Detrimental Solids removal unit (DSRU) itself may be stand alone orit may be incorporated into the reactor vessel as guard bed. Whenincorporated into a reactor vessel, the DSRU may be one or more denselypacked beds of inert catalyst material or other solids that act asfilter media. As a stand alone unit, the DSRU may be a reactor vesselwith multiple densely packed beds of filterting materials such as inertcatalysts or it may be as described in U.S. Pat. No. 5,074,989 whichcomprises a filtration module with a plurality of filtration barriersaligned the length of the filtration cell. The filtrate is that portionof the feedstock passing through the filtration barriers, preferablyfrom interior to exterior driven by a pressure drop across thefiltration barriers. The filtration barriers may be mineral basedfiltration barriers such as those disclosed in U.S. Pat. No. 5,074,989,or they may be porous sintered metal filters or a combination of thetwo. The porosity of the filtration barriers is characterized by thepermeametric radii of the pores. This reflects size of pores and thediameter of particles that can transit the filtration barrier.Commercially available mineral barriers having a permeametric radii from2-100 nm (ultrafiltration) and 0.1-100 microns (microfiltration) will beuseful. One of skilled in the art will also appreciate that staging thefiltration barriers so the HMFO is first microfiltered followed byultrafiltration will prolong the life of the filter and maximize theefficiency of the DSRU. Construction of a DSRU, which may operate atrelatively pressures lower than 2 MPa, and temperatures equal to orlower than 300° C., adopted in this process would not present technicaldifficulties for an experienced technician in this field

In this description, items already described above as part of the coreprocess have retained the same numbering and designation for ease ofdescription. As show in FIG. 2 , a DSRU 3 can be utilized to pre-treatthe Feedstock HMFO prior to mixing with the Activating Gas 4 as part ofthe core process disclosed above. While simplistically represented inthis drawing, the DSRU 3 may be multiple parallel or in series DSRUshowever the DSRU may be as simple as a single reactor vessel in whichthe HMFO is filtered through a bed of inert or inactive catalystmaterials prior to exposure to the reactors containing active catalystmaterials. While a single a fixed bed, flow through/contact vessel maybe used, it may be advantageous and it is preferable to have multiplecontact vessels in parallel with each other to allow for one unit to beactive while a second or third unit are being reloaded. Such anarrangement involving multiple parallel contact vessels withpipes/switching valves, etc. . . . is well within the abilities of oneof skill in the art of refinery process design and operation.

Product HMFO The Product HFMO resulting from the disclosed illustrativeprocess is of merchantable quality for sale and use as a heavy marinefuel oil (also known as a residual marine fuel oil or heavy bunker fuel)and exhibits the bulk physical properties required for the Product HMFOto be an ISO compliant (i.e. ISO8217:2017) residual marine fuel oil. TheProduct HMFO will exhibit bulk properties of: a kinematic viscosity at50° C. (ISO 3104) between the range from 180 mm²/s to 700 mm²/s; adensity at 15° C. (ISO 3675) between the range of 991.0 kg/m³ to 1010.0kg/m³; a CCAI in the range of 780 to 870; a flash point (ISO 2719) nolower than 60° C.; a total sediment—aged (ISO 10307-2) of less than0.10% wt.; a carbon residue—micro method (ISO 10370) less than 20.00%wt. and preferably less than 18%, and a aluminum plus silicon (ISO10478) content less than 60 mg/kg.

The Product HMFO has a sulfur content (ISO 14596 or ISO 8754) less than0.5 wt % and preferably less than 0.1% wt. and complies with the IMOAnnex VI (revised) requirements for a low sulfur and preferably anultra-low sulfur HMFO. That is the sulfur content of the Product HMFOhas been reduced by about 80% or greater when compared to the FeedstockHMFO. Similarly, the vanadium content (ISO 14597) of the Product HeavyMarine Fuel Oil is less than 20% and more preferably less than 1% of themaximum vanadium content of the Feedstock Heavy Marine Fuel Oil. One ofskill in the art will appreciate that a substantial reduction in sulfurand vanadium content of the Feedstock HMFO indicates a process havingachieved a substantial reduction in the Environmental Contaminates fromthe Feedstock HMFO; of equal importance is this has been achieved whilemaintaining the desirable properties of an ISO 8217 (2017) compliantHMFO.

The Product HMFO not only complies with ISO 8217 (2017) (and ismerchantable as a residual marine fuel oil or bunker fuel), the ProductHMFO has a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt. preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05% wt. ppm and 0.5% wt. and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1% wt. and 0.5% wt. The vanadium content of the Product HMFO is wellwithin the maximum vanadium content (ISO 14597) required for an ISO 8217(2017) residual marine fuel oil exhibiting a vanadium content lower than450 ppm mg/kg, preferably a vanadium content (ISO 14597) lower than 300mg/kg and more preferably a vanadium content (ISO 14597) less than 50mg/kg.

One knowledgeable in the art of marine fuel blending, bunker fuelformulations and the fuel logistical requirements for marine shippingfuels will readily appreciate that without further compositional changesor blending, the Product HMFO can be sold and used as a low sulfurMARPOL Annex VI compliant heavy (residual) marine fuel oil that is adirect substitute for the high sulfur heavy (residual) marine fuel oilor heavy bunker fuel currently in use. One illustrative embodiment is anISO 8217 (2017) compliant low sulfur heavy marine fuel oil comprising(and preferably consisting essentially of) a hydroprocessed ISO 8217(2017) compliant high sulfur heavy marine fuel oil, wherein the sulfurlevels of the hydroprocessed ISO 8217 (2017) compliant high sulfur heavymarine fuel oil is greater than 0.5% wt. and wherein the sulfur levelsof the ISO 8217 (2017) compliant low sulfur heavy marine fuel oil isless than 0.5% wt. Another illustrative embodiment is an ISO 8217 (2017)compliant ultra-low sulfur heavy marine fuel oil comprising (andpreferably consisting essentially of) a 100% hydroprocessed ISO 8217(2017) compliant high sulfur heavy marine fuel oil, wherein the sulfurlevels of the hydroprocessed ISO 8217 (2017) compliant high sulfur heavymarine fuel oil is greater than 0.5% wt. and wherein the sulfur levelsof the ISO 8217 (2017) compliant low sulfur heavy marine fuel oil isless than 0.1% wt.

Because of the present invention, multiple economic and logisticalbenefits to the bunkering and marine shipping industries can berealized. The benefits include minimal changes to the existing heavymarine fuel bunkering infrastructure (storage and transferring systems);minimal changes to shipboard systems are needed to comply with emissionsrequirements of MARPOL Annex VI no additional training or certificationsfor crew members will be needed, amongst the realizable benefits.Refiners will also realize multiple economic and logistical benefits,including: no need to alter or rebalance the refinery operations andproduct streams to meet a new market demand for low sulfur or ultralowsulfur HMFO; no additional units are needed in the refinery withadditional hydrogen or sulfur capacity because the illustrative processcan be conducted as a stand-alone unit; refinery operations can remainfocused on those products that create the greatest value from the crudeoil received (i.e. production of petrochemicals, gasoline and distillate(diesel); refiners can continue using the existing slates of crude oilswithout having to switch to sweeter or lighter crudes to meet theenvironmental requirements for HMFO products.

Heavy Marine Fuel Composition

One aspect of the present inventive concept is a fuel compositioncomprising, but preferably consisting essentially of, the Product HMFOresulting from the processes disclosed, and may optionally includeDiluent Materials. The bulk properties of the Product HMFO itselfcomplies with ISO 8217 (2017) and meets the global IMO Annex VIrequirements for maximum sulfur content (ISO 14596 or ISO 8754). Ifultra low levels of sulfur are desired, the process of the presentinvention achieves this and one of skill in the art of marine fuelblending will appreciate that a low sulfur or ultra-low sulfur ProductHMFO can be utilized as a primary blending stock to form a global IMOAnnex VI compliant low sulfur Heavy Marine Fuel Composition. Such a lowsulfur Heavy Marine Fuel Composition will comprise (and preferablyconsist essentially of): a) the Product HMFO and b) Diluent Materials.In one embodiment, the majority of the volume of the Heavy Marine FuelComposition is the Product HMFO with the balance of materials beingDiluent Materials. Preferably, the Heavy Marine Fuel Composition is atleast 75% by volume, preferably at least 80% by volume, more preferablyat least 90% by volume, and furthermore preferably at least 95% byvolume Product HMFO with the balance being Diluent Materials.

Diluent Materials may be hydrocarbon or non-hydrocarbon based materialsmixed into or combined with or added to, or solid particle materialssuspended in, the Product HMFO. The Diluent Materials may intentionallyor unintentionally alter the composition of the Product HMFO but not sothe resulting mixture violates the ISO 8217 (2017) standards for thebulk properties of residual marine fuels or fails to have a sulfurcontent lower than the global MARPOL standard of 0.5% wt. sulfur (ISO14596 or ISO 8754). Examples of Diluent Materials considered hydrocarbonbased materials include: Feedstock HMFO (i.e. high sulfur HMFO);distillate based fuels such as road diesel, gas oil, MGO or MDO; cutteroil (which is used in formulating residual marine fuel oils); renewableoils and fuels such as biodiesel, methanol, ethanol; synthetichydrocarbons and oils based on gas to liquids technology such asFischer-Tropsch derived oils, synthetic oils such as those based onpolyethylene, polypropylene, dimer, trimer and poly butylene; refineryresidues or other hydrocarbon oils such as atmospheric residue, vacuumresidue, fluid catalytic cracker (FCC) slurry oil, FCC cycle oil,pyrolysis gasoil, cracked light gas oil (CLGO), cracked heavy gas oil(CHGO), light cycle oil (LCO), heavy cycle oil (HCO), thermally crackedresidue, coker heavy distillate, bitumen, de-asphalted heavy oil,visbreaker residue, slop oils, asphaltinic oils; used or recycled motoroils; lube oil aromatic extracts and crude oils such as heavy crude oil,distressed crude oils and similar materials that might otherwise be sentto a hydrocracker or diverted into the blending pool for a prior arthigh sulfur heavy (residual) marine fuel oil. Examples of DiluentMaterials considered non-hydrocarbon based materials include: residualwater (i.e. water absorbed from the humidity in the air or water that ismiscible or solubilized, sometimes as microemulsions, into thehydrocarbons of the Product HMFO), fuel additives which can include, butare not limited to detergents, viscosity modifiers, pour pointdepressants, lubricity modifiers, de-hazers (e.g. alkoxylated phenolformaldehyde polymers), antifoaming agents (e.g. polyether modifiedpolysiloxanes); ignition improvers; anti rust agents (e.g. succinic acidester derivatives); corrosion inhibitors; anti-wear additives,anti-oxidants (e.g. phenolic compounds and derivatives), coating agentsand surface modifiers, metal deactivators, static dissipating agents,ionic and nonionic surfactants, stabilizers, cosmetic colorants andodorants and mixtures of these. A third group of Diluent Materials mayinclude suspended solids or fine particulate materials that are presentbecause of the handling, storage and transport of the Product HMFO orthe Heavy Marine Fuel Composition, including but not limited to: carbonor hydrocarbon solids (e.g. coke, graphitic solids, ormicro-agglomerated asphaltenes), iron rust and other oxidative corrosionsolids, fine bulk metal particles, paint or surface coating particles,plastic or polymeric or elastomer or rubber particles (e.g. resultingfrom the degradation of gaskets, valve parts, etc. . . . ), catalystfines, ceramic or mineral particles, sand, clay, and other earthenparticles, bacteria and other biologically generated solids, andmixtures of these that may be present as suspended particles, butotherwise don't detract from the merchantable quality of the HeavyMarine Fuel Composition as an ISO 8217 (2017) compliant heavy (residual)marine fuel.

The blend of Product HMFO and Diluent Materials must be of merchantablequality as a low sulfur heavy (residual) marine fuel. That is the blendmust be suitable for the intended use as heavy marine bunker fuel andgenerally be fungible as a bunker fuel for ocean going ships. Preferablythe Heavy Marine Fuel Composition must retain the bulk physicalproperties required of an ISO 8217 (2017) compliant residual marine fueloil and a sulfur content lower than the global MARPOL standard of 0.5%wt. sulfur (ISO 14596 or ISO 8754) so that the material qualifies asMARPOL Annex VI Low Sulfur Heavy Marine Fuel Oil (LS-HMFO). The sulfurcontent of the Product HMFO can be lower than 0.5% wt. (i.e. below 0.1%wt sulfur (ISO 14596 or ISO 8754)) to qualify as a MARPOL Annex VIcompliant Ultra-Low Sulfur Heavy Marine Fuel Oil (ULS-HMFO) and a HeavyMarine Fuel Composition likewise can be formulated to qualify as aMARPOL Annex VI compliant ULS-HMFO suitable for use as marine bunkerfuel in the ECA zones. To qualify as an ISO 8217 (2017) qualified fuel,the Heavy Marine Fuel Composition of the present invention must meetthose internationally accepted standards.

Production Plant Description:

Turning now to a more detailed illustrative embodiment of a productionplant implementing both the core process and the DSRU disclosed, FIG. 4show a schematic for a production plant implementing the core processdescribed above combined with a pre-DSRU (FIG. 4 , item 2) which willreduce Detrimental Solids in a Feedstock HMFO to produce a Product HMFOthat is ISO 8217:2017 compliant and with the desired properties of a lowDetrimental Solids content.

It will be appreciated by one of skill in the art that additionalalternative embodiments for the core process and the DSRU may involvemultiple vessels and reactors even though only one of each is shown.Variations using multiple vessels/reactors are contemplated by thepresent invention but are not illustrated in greater detail forsimplicity sake.

The Reactor System (11) for the core process is described in greaterdetail below and using multiple vessels process has been described. Itwill be noted by one of skill in the art that in FIGS. 4 and 5 ,portions of the production plant with similar function and operationhave been assigned the same reference number. This has been done forconvenience and succinctness only and differences between FIG. 4 areduly noted and explained below.

The Feedstock HMFO (A) is fed from outside the battery limits (OSBL) tothe Oil Feed Surge Drum (1) that receives feed from outside the batterylimits (OSBL) and provides surge volume adequate to ensure smoothoperation of the unit. Water entrained in the feed is removed from theHMFO with the water being discharged a stream (1 c) for treatment OSBL.

As shown in FIG. 4 , the Feedstock HMFO (A) is withdrawn from the OilFeed Surge Drum (1) via line (1 b) by the Oil Feed Pump (3) and sent tothe DSRU (2) as a pretreatment step. The pre-treated Feedstock HMFO ispressurized to a pressure required for the process. The pressurized HMFO(A′) then passes through line (3 a) to the Oil Feed/Product HeatExchanger (5) where the pressurized HMFO (A′) is partially heated by theProduct HMFO (B). The pressurized Feedstock HMFO (A′) passing throughline (5 a) is further heated against the effluent from the ReactorSystem (E) in the Reactor Feed/Effluent Heat Exchanger (7).

The heated and pressurized Feedstock HMFO (A″) in line (7 a) is thenmixed with Activating Gas (C) provided via line (23 c) at Mixing Point(X) to form a Feedstock Mixture (D). The mixing point (X) can be anywell know gas/liquid mixing system or entrainment mechanism well knownto one skilled in the art.

The Feedstock Mixture (D) passes through line (9 a) to the Reactor FeedFurnace (9) where the Feedstock Mixture (D) is heated to the specifiedprocess temperature. The Reactor Feed Furnace (9) may be a fired heaterfurnace or any other kind to type of heater as known to one of skill inthe art if it will raise the temperature of the Feedstock mixture to thedesired temperature for the process conditions.

The heated Feedstock Mixture (D′) exits the Reactor Feed Furnace (9) vialine 9 b and is fed into the Reactor System (11). The heated FeedstockMixture (D′) enters the Reactor System (11) where environmentalcontaminates, such a sulfur, nitrogen, and metals are preferentiallyremoved from the Feedstock HMFO component of the heated FeedstockMixture. The Reactor System contains a catalyst which preferentiallyremoves the sulfur compounds in the Feedstock HMFO component by reactingthem with hydrogen in the Activating Gas to form hydrogen sulfide. TheReactor System will also achieve demetallization, denitrogenation, and acertain amount of ring opening hydrogenation of the complex aromaticsand asphaltenes, however minimal hydrocracking of hydrocarbons shouldtake place. The process conditions of hydrogen partial pressure,reaction pressure, temperature and residence time as measured by Liquidhourly velocity are optimized to achieve desired final product quality.A more detailed discussion of the Reactor System, the catalyst, theprocess conditions, and other aspects of the process are contained belowin the “Reactor System Description.”

The Reactor System Effluent (E) exits the Reactor System (11) via line(11 a) and exchanges heat against the pressurized and partially heatsthe Feedstock HMFO (A′) in the Reactor Feed/Effluent Exchanger (7). Thepartially cooled Reactor System Effluent (E′) then flows via line (11 c)to the Hot Separator (13).

The Hot Separator (13) separates the gaseous components of the ReactorSystem Effluent (F) which are directed to line (13 a) from the liquidcomponents of the Reactor System effluent (G) which are directed to line(13 b). The gaseous components of the Reactor System effluent in line(13 a) are cooled against air in the Hot Separator Vapor Air Cooler (15)and then flow via line (15 a) to the Cold Separator (17).

The Cold Separator (17) further separates any remaining gaseouscomponents from the liquid components in the cooled gaseous componentsof the Reactor System Effluent (F′). The gaseous components from theCold Separator (F″) are directed to line (17 a) and fed onto the AmineAbsorber (21). The Cold Separator (17) also separates any remaining ColdSeparator hydrocarbon liquids (H) in line (17 b) from any Cold Separatorcondensed liquid water (I). The Cold Separator condensed liquid water(I) is sent OSBL via line (17 c) for treatment.

The hydrocarbon liquid components of the Reactor System effluent fromthe Hot Separator (G) in line (13 b) and the Cold Separator hydrocarbonliquids (H) in line (17 b) are combined and are fed to the Oil ProductStripper System (19). The Oil Product Stripper System (19) removes anyresidual hydrogen and hydrogen sulfide from the Product HMFO (B) whichis discharged in line (19 b) to storage OSBL. It is also contemplatedthat a second draw (not shown) may be included to withdraw a distillateproduct, preferably a middle to heavy distillate. The vent stream (M)from the Oil Product Stripper in line (19 a) may be sent to the fuel gassystem or to the flare system that are OSBL.

An alternative embodiment not shown in FIG. 5 , but well within theskill of one in the art, would be to relocate the DSRU (18) from theline prior to the Oil Product Stripper (19) to a location downstream ofthe Oil Product Stripper (19). Such a relocation of the DSRU (18) toline (19 b) will allow for the Detrimental Solids removal from the finalproduct HMFO prior to being sent to storage OSBL. This location ispracticable because the DSRU enhances the value of the Product HMFOwithout adversely impacting the desirable properties of the ProductHMFO. The DRSU may also impart an additional amount of stability to theProduct HMFO by removing the micron sized solids that may promote theformation of asphaltene solids or paraffinic solids.

The gaseous components from the Cold Separator (F″) in line (17 a)contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons(mostly methane and ethane). This vapor stream (17 a) feeds an AmineAbsorber (21) where it is contacted against Lean Amine (J) provided OSBLvia line (21 a) to the Amine Absorber (21) to remove hydrogen sulfidefrom the gases making up the Activating Gas recycle stream (C′). Richamine (K) which has absorbed hydrogen sulfide exits the bottom of theAmine Absorber (21) and is sent OSBL via line (21 b) for amineregeneration and sulfur recovery.

The Amine Absorber overhead vapor in line (21 c) is preferably recycledto the process as a Recycle Activating Gas (C′) via the RecycleCompressor (23) and line (23 a) where it is mixed with the MakeupActivating Gas (C″) provided OSBL by line (23 b). This mixture ofRecycle Activating Gas (C′) and Makeup Activating Gas (C″) to form theActivating Gas (C) utilized in the process via line (23 c) as notedabove. A Scrubbed Purge Gas stream (H) is taken from the Amine Absorberoverhead vapor line (21 c) and sent via line (21 d) to OSBL to preventthe buildup of light hydrocarbons or other non-condensables.

Reactor System Description:

The core process Reactor System (11) illustrated in FIG. 4 comprises asingle reactor vessel loaded with the process catalyst and sufficientcontrols, valves and sensors as one of skill in the art would readilyappreciate.

Alternative Reactor Systems in which more than one reactor vessel may beutilized in parallel or in a cascading series can easily be substitutedfor the single reactor vessel Reactor System 11 shown. In such anembodiment, each reactor vessel is similarly loaded with processcatalyst and can be provided the heated Feed Mixture (D′) via a commonline. The effluent from each of the three reactors is recombined in lineand forms a combined Reactor Effluent (E) for further processing asdescribed above. The illustrated arrangement will allow the threereactors to carry out the process effectively multiplying the hydrauliccapacity of the overall Reactor System. Control valves and isolationvalves may also prevent feed from entering one reactor vessel but notanother reactor vessel. In this way one reactor can be by-passed andplaced off-line for maintenance and reloading of catalyst while theremaining reactors continues to receive heated Feedstock Mixture (D′).It will be appreciated by one of skill in the art this arrangement ofreactor vessels in parallel is not limited in number to three, butmultiple additional reactor vessels can be added. The only limitation tothe number of parallel reactor vessels is plot spacing and the abilityto provide heated Feedstock Mixture (D′) to each active reactor.

In another illustrative embodiment cascading reactor vessels are loadedwith process catalyst with the same or different activities towardmetals, sulfur or other environmental contaminates to be removed. Forexample, one reactor may be loaded with a highly active demetallizationcatalyst, a second subsequent or downstream reactor may be loaded with abalanced demetallization/desulfurizing catalyst, and reactor downstreamfrom the second reactor may be loaded with a highly activedesulfurization catalyst. This allows for greater control and balance inprocess conditions (temperature, pressure, space flow velocity, etc. . .. ) so it is tailored for each catalyst. In this way one can optimizethe parameters in each reactor depending upon the material being fed tothat specific reactor/catalyst combination and minimize thehydrocracking reactions. As with the prior illustrative embodiment,multiple cascading series of reactors can be utilized in parallel and inthis way the benefits of such an arrangement noted above (i.e. allow oneseries to be “online” while the other series is “off line” formaintenance or allow increased plant capacity).

The reactor(s) that form the Reactor System may be fixed bed, ebulliatedbed or slurry bed or a combination. As envisioned, fixed bed reactorsare preferred as these are easier to operate and maintain.

The reactor vessel in the Reactor System is loaded with one or moreprocess catalysts. The exact design of the process catalyst system is afunction of feedstock properties, product requirements and operatingconstraints and optimization of the process catalyst can be carried outby routine trial and error by one of ordinary skill in the art.

The process catalyst(s) comprise at least one metal selected from thegroup consisting of the metals each belonging to the groups 6, 8, 9 and10 of the Periodic Table, and more preferably a mixed transition metalcatalyst such as Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo are utilized. The metalis preferably supported on a porous inorganic oxide catalyst carrier.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The preferred porous inorganicoxide catalyst carrier is alumina. The pore size and metal loadings onthe carrier may be systematically varied and tested with the desiredfeedstock and process conditions to optimize the properties of theProduct HMFO. Such activities are well known and routine to one of skillin the art. Catalyst in the fixed bed reactor(s) may be dense-loaded orsock-loaded.

The catalyst selection utilized within and for loading the ReactorSystem may be preferential to desulfurization by designing a catalystloading scheme that results in the Feedstock mixture first contacting acatalyst bed that with a catalyst preferential to demetallizationfollowed downstream by a bed of catalyst with mixed activity fordemetallization and desulfurization followed downstream by a catalystbed with high desulfurization activity. In effect the first bed withhigh demetallization activity acts as a guard bed for thedesulfurization bed.

The objective of the Reactor System is to treat the Feedstock HMFO atthe severity required to meet the Product HMFO specification.Demetallization, denitrogenation and hydrocarbon hydrogenation reactionsmay also occur to some extent when the process conditions are optimizedso performing the Reactor System achieves the required level ofdesulfurization. Hydrocracking is preferably minimized to reduce thevolume of hydrocarbons formed as by-product hydrocarbons to the process.The objective of the process is to selectively remove the environmentalcontaminates from Feedstock HMFO and minimize the formation ofunnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

The process reactive conditions in each reactor vessel will depend uponthe feedstock, the catalyst utilized and the desired final properties ofthe Product HMFO desired. Variations in reactive conditions are to beexpected by one of ordinary skill in the art and these may be determinedby pilot plant testing and systematic optimization of the process. Withthis in mind it has been found that the operating pressure, theindicated operating temperature, the ratio of the Activating Gas toFeedstock HMFO, the partial pressure of hydrogen in the Activating Gasand the space velocity all are important parameters to consider. Theoperating pressure of the Reactor System should be in the range of 250psig and 3000 psig, preferably between 1000 psig and 2500 psig and morepreferably between 1500 psig and 2200 psig. The indicated operatingtemperature of the Reactor System should be 500° F. to 900° F.,preferably between 650° F. and 850° F. and more preferably between 680°F. and 800° F. The ratio of the quantity of the Activating Gas to thequantity of Feedstock HMFO should be in the range of 250 scf gas/bbl ofFeedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO, preferablybetween 2000 scf gas/bbl of Feedstock HMFO to 5000 scf gas/bbl ofFeedstock HMFO and more preferably between 2500 scf gas/bbl of FeedstockHMFO to 4500 scf gas/bbl of Feedstock HMFO. The Activating Gas should beselected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane, so Activating Gas has an ideal gas partial pressureof hydrogen (p_(H2)) greater than 80% of the total pressure of theActivating Gas mixture (P) and preferably wherein the Activating Gas hasan ideal gas partial pressure of hydrogen (p_(H2)) greater than 95% ofthe total pressure of the Activating Gas mixture (P). The Activating Gasmay have a hydrogen mole fraction in the range between 80% of the totalmoles of Activating Gas mixture and more preferably wherein theActivating Gas has a hydrogen mole fraction between 80% and 99% of thetotal moles of Activating Gas mixture. The liquid hourly space velocitywithin the Reactor System should be between 0.05 oil/hour/m³ catalystand 1.0 oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³catalyst and 0.5 oil/hour/m³ catalyst and more preferably between 0.1oil/hour/m³ catalyst and 0.3 oil/hour/m³ catalyst to achieve deepdesulfurization with product sulfur levels below 0.1 ppmw.

The hydraulic capacity rate of the Reactor System should be between 100bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day. The desired hydraulic capacity may be achieved in a singlereactor vessel Reactor System or in a multiple reactor vessel ReactorSystem.

These examples will provide one skilled in the art with a more specificillustrative embodiment for conducting the process disclosed and claimedherein:

Example 1

Overview:

The purpose of a pilot test run is to demonstrate that feedstock HMFOcan be processed through a reactor loaded with commercially availablecatalysts at specified conditions to remove environmental contaminates,specifically sulfur and other contaminants from the HMFO to produce aproduct HMFO that is MARPOL compliant, that is production of a LowSulfur Heavy Marine Fuel Oil (LS-HMFO) or Ultra-Low Sulfur Heavy MarineFuel Oil (USL-HMFO).

Pilot Unit Set Up:

The pilot unit will be set up with two 434 cm³ reactors arranged inseries to process the feedstock HMFO. The lead reactor will be loadedwith a blend of a commercially available hydro-demetaling (HDM) catalystand a commercially available hydro-transition (HDT) catalyst. One ofskill in the art will appreciate that the HDT catalyst layer may beformed and optimized using a mixture of HDM and HDS catalysts combinedwith an inert material to achieve the desired intermediate/transitionactivity levels. The second reactor will be loaded with a blend of thecommercially available hydro-transition (HDT) and a commerciallyavailable hydrodesulfurization (HDS). One can load the second reactorsimply with a commercially hydrodesulfurization (HDS) catalyst. One ofskill in the art will appreciate that the specific feed properties ofthe Feedstock HMFO may affect the proportion of HDM, HDT and HDScatalysts in the reactor system. A systematic process of testingdifferent combinations with the same feed will yield the optimizedcatalyst combination for any feedstock and reaction conditions. For thisexample, the first reactor will be loaded with ⅔ hydro-demetalingcatalyst and ⅓ hydro-transition catalyst. The second reactor will beloaded with all hydrodesulfurization catalyst. The catalysts in eachreactor will be mixed with glass beads (approximately 50% by volume) toimprove liquid distribution and better control reactor temperature. Forthis pilot test run, one should use these commercially availablecatalysts: HDM: Albemarle KFR 20 series or equivalent; HDT: AlbemarleKFR 30 series or equivalent; HDS: Albemarle KFR 50 or KFR 70 orequivalent. Once set up of the pilot unit is complete, the catalyst canbe activated by sulfiding the catalyst using dimethyldisulfide (DMDS) ina manner well known to one of skill in the art.

Pilot Unit Operation:

Upon completion of the activating step, the pilot unit will be ready toreceive the feedstock HMFO and Activating Gas feed. For the presentexample, the Activating Gas can be technical grade or better hydrogengas. The mixed Feedstock HMFO and Activating Gas will be provided to thepilot plant at rates and operating conditions as specified: Oil FeedRate: 108.5 ml/h (space velocity=0.25/h); Hydrogen/Oil Ratio: 570 Nm3/m3(3200 scf/bbl); Reactor Temperature: 372° C. (702° F.); Reactor OutletPressure:13.8 MPa(g) (2000 psig).

One of skill in the art will know that the rates and conditions may besystematically adjusted and optimized depending upon feed properties toachieve the desired product requirements. The unit will be brought to asteady state for each condition and full samples taken so analyticaltests can be completed. Material balance for each condition should beclosed before moving to the next condition.

Expected impacts on the Feedstock HMFO properties are: Sulfur Content(wt %): Reduced by at least 80%; Metals Content (wt %): Reduced by atleast 80%; MCR/Asphaltene Content (wt %): Reduced by at least 30%;Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%. 078. Process conditionsin the Pilot Unit can be systematically adjusted as per Table 4 toassess the impact of process conditions and optimize the performance ofthe process for the specific catalyst and feedstock HMFO utilized.

TABLE 4 Optimization of Process Conditions HC Feed Rate (ml/h), Nm³H₂/m³ oil/ Temp Pressure Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.) (MPa(g)/psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8/2000 T1 108.5[0.25] 570/3200 362/684 13.8/2000 T2 108.5 [0.25] 570/3200 382/72013.8/2000 L1 130.2 [0.30] 570/3200 372/702 13.8/2000 L2  86.8 [0.20]570/3200 372/702 13.8/2000 H1 108.5 [0.25] 500/2810 372/702 13.8/2000 H2108.5 [0.25] 640/3590 372/702 13.8/2000 S1  65.1 [0.15] 620/3480 385/72515.2/2200

In this way, the conditions of the pilot unit can be optimized toachieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt.sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt.sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (spacevelocity=0.15/h); Hydrogen/Oil Ratio: 620 Nm³/m³ (3480 scf/bbl); ReactorTemperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200psig)

Table 5 summarizes the anticipated impacts on key properties of HMFO.

TABLE 5 Expected Impact of Process on Key Properties of HMFO PropertyMinimum Typical Maximum Sulfur Conversion/Removal 80% 90% 98% MetalsConversion/Removal 80% 90% 100%  MCR Reduction 30% 50% 70% AsphalteneReduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through NaphthaYield 0.5%  1.0%  4.0%  Hydrogen Consumption (scf/bbl) 500 750 1500

Table 6 lists analytical tests to be carried out for thecharacterization of the Feedstock HMFO and Product HMFO. The analyticaltests include those required by ISO for the Feedstock HMFO and theproduct HMFO to qualify and trade in commerce as ISO compliant residualmarine fuels. The additional parameters are provided so that one skilledin the art can understand and appreciate the effectiveness of theinventive process.

TABLE 6 Analytical Tests and Testing Procedures Sulfur Content ISO 8754or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185Kinematic Viscosity @ 50° C. ISO 3104 Pour Point, ° C. ISO 3016 FlashPoint, ° C. ISO 2719 CCAI ISO 8217, ANNEX B Ash Content ISO 6245 TotalSediment - Aged ISO 10307-2 Micro Carbon Residue, mass % ISO 10370 H2S,mg/kg IP 570 Acid Number ASTM D664 Water ISO 3733 Specific ContaminantsIP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zincor IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:HRatio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt % ASTM D6560Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID GasChromatography or comparable

Table 7 contains the Feedstock HMFO analytical test results and theProduct HMFO analytical test results expected from the inventive processthat indicate the production of a LS HMFO. It will be noted by one ofskill in the art that under the conditions, the levels of hydrocarboncracking will be minimized to levels substantially lower than 10%, morepreferably less than 5% and even more preferably less than 1% of thetotal mass balance.

TABLE 7 Analytical Results Feedstock HMFO Product HMFO Sulfur Content,mass % 3.0   0.3 Density @ 15 C., kg/m³ 990 950⁽¹⁾  Kinematic Viscosity@ 50 C., mm²/s 380 100⁽¹⁾  Pour Point, ° C. 20 10  Flash Point, ° C. 110100⁽¹⁾  CCAI 850 820  Ash Content, mass % 0.1   0.0 Total Sediment -Aged, mass % 0.1   0.0 Micro Carbon Residue, mass % 13.0   6.5 H2S,mg/kg 0 0 Acid Number, mg KO/g 1   0.5 Water, vol % 0.5 0 SpecificContaminants, mg/kg Vanadium 180 20  Sodium 30 1 Aluminum 10 1 Silicon30 3 Calcium 15 1 Zinc 7 1 Phosphorous 2 0 Nickle 40 5 Iron 20 2Distillation, ° C./° F. IBP 160/320  120/248  5% wt 235/455  225/437 10%wt 290/554  270/518 30% wt 410/770  370/698 50% wt 540/1004 470/878 70%wt 650/1202  580/1076 90% wt 735/1355  660/1220 FBP 820/1508  730/1346C:H Ratio (ASTM D3178) 1.2   1.3 SARA Analysis Saturates 16 22 Aromatics 50 50  Resins 28 25  Asphaltenes 6 3 Asphaltenes, wt % 6.0  2.5 Total Nitrogen, mg/kg 4000 3000   Note: ⁽¹⁾property will beadjusted to a higher value by post process removal of light material viadistillation or stripping from product HMFO.

The product HMFO produced by the inventive process will reach ULS HMFOlimits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation ofthe process parameters, for example by a lower space velocity or byusing a Feedstock HMFO with a lower initial sulfur content.

Example 2: RMG-380 HMFO

Pilot Unit Set Up:

A pilot unit was set up as noted above in Example 1 with these changes:the first reactor was loaded with: as the first (upper) layerencountered by the feedstock 70% vol Albemarle KFR 20 serieshydro-demetaling catalyst and 30% vol Albemarle KFR 30 serieshydro-transition catalyst as the second (lower) layer. The secondreactor was loaded with 20% Albemarle KFR 30 series hydrotransitioncatalyst as the first (upper) layer and 80% vol hydrodesulfurizationcatalyst as the second (lower) layer. The catalyst was activated bysulfiding the catalyst with dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation:

Upon completion of the activating step, the pilot unit was ready toreceive the feedstock HMFO and Activating Gas feed. The Activating Gaswas technical grade or better hydrogen gas. The Feedstock HMFO was acommercially available and merchantable ISO 8217 (2017) compliant HMFO,except for a high sulfur content (2.9 wt %). The mixed Feedstock HMFOand Activating Gas was provided to the pilot plant at rates andconditions as specified in Table 8 below. The conditions were varied tooptimize the level of sulfur in the product HMFO material.

TABLE 8 Process Conditions Product HC Feed Pressure HMFO Rate (ml/h),Nm³ H₂/m³ oil/ Temp (MPa (g)/ Sulfur Case [LHSV(/h)] scf H₂/bbl oil (°C./° F.) psig) % wt. Base- 108.5 [0.25] 570/3200 371/700 13.8/2000 0.24line T1 108.5 [0.25] 570/3200 362/684 13.8/2000 0.53 T2 108.5 [0.25]570/3200 382/720 13.8/2000 0.15 L1 130.2 [0.30] 570/3200 372/70213.8/2000 0.53 S1  65.1 [0.15] 620/3480 385/725 15.2/2200 0.10 P1 108.5[0.25] 570/3200 371/700    /1700 0.56 T2/P1 108.5 [0.25] 570/3200382/720    /1700 0.46

Analytical data for a representative sample of the feedstock HMFO andrepresentative samples of product HMFO are below:

TABLE 7 Analytical Results - HMFO (RMG-380) Feedstock Product ProductSulfur Content, mass % 2.9 0.3 0.1 Density @ 15° C., kg/m³ 988 932 927Kinematic Viscosity @ 50° C., mm²/s 382 74 47 Pour Point, ° C. −3 −12−30 Flash Point, ° C. 116 96 90 CCAI 850 812 814 Ash Content, mass %0.05 0.0 0.0 Total Sediment - Aged, mass % 0.04 0.0 0.0 Micro CarbonResidue, mass % 11.5 3.3 4.1 H2S, mg/kg 0.6 0 0 Acid Number, mg KO/g 0.30.1 >0.05 Water, vol % 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium138 15 <1 Sodium 25 5 2 Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1Zinc 5 <1 <1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 Distillation,° C./° F. IBP 178/352 168/334 161/322  5% wt 258/496 235/455 230/446 10%wt 298/569 270/518 264/507 30% wt 395/743 360/680 351/664 50% wt 517/962461/862 439/822 70% wt  633/1172  572/1062  552/1026 90% wt  >720/>1328 694/1281  679/1254 FBP  >720/>1328  >720/>1328  >720/>1328 C:H Ratio(ASTM D3178) 1.2 1.3 1.3 SARA Analysis Saturates 25.2 28.4 29.4Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1Asphaltenes, wt % 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

In Table 7, both feedstock HMFO and product HMFO exhibited observed bulkproperties consistent with ISO 8217 (2017) for a merchantable residualmarine fuel oil, except that the sulfur content of the product HMFO wasreduced as noted above when compared to the feedstock HMFO.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved not only an ISO 8217(2017) compliant LS HMFO (i.e. 0.5% wt. sulfur) but also an ISO 8217(2017) compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.

Example 3: RMK-500 HMFO

The feedstock to the pilot reactor utilized in example 2 above waschanged to a commercially available and merchantable ISO 8217 (2017)RMK-500 compliant HMFO, except that it has high environmentalcontaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of theRMK-500 feedstock high sulfur HMFO are provide below:

TABLE 8 Analytical Results- Feedstock HMFO (RMK-500) Sulfur Content,mass % 3.3 Density @ 15° C., kg/m³ 1006 Kinematic Viscosity @ 50° C.,mm²/s 500

The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided tothe pilot plant at rates and conditions and the resulting sulfur levelsachieved in the table below

TABLE 9 Process Conditions HC Feed Rate Product (ml/h), Nm³ H₂/m³ oil/Temp Pressure (RMK-500) Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.)(MPa(g)/psig) sulfur % wt. A 108.5 [0.25]  640/3600 377/710 13.8/20000.57 B 95.5 [0.22] 640/3600 390/735 13.8/2000 0.41 C 95.5 [0.22]640/3600 390/735 11.7/1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3/15000.61 E 95.5 [0.22] 640/3600 393/740 17.2/2500 0.37 F 95.5 [0.22]640/3600 393/740  8.3/1200 0.70 G 95.5 [0.22] 640/3600 416/780  8.3/1200

The resulting product (RMK-500) HMFO exhibited observed bulk propertiesconsistent with the feedstock (RMK-500) HMFO, except that the sulfurcontent was reduced as noted in the above table.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved a LS HMFO (i.e. 0.5% wt.sulfur) product HMFO having bulk characteristics of a ISO 8217 (2017)compliant RMK-500 residual fuel oil. It will also be appreciated thatthe process can be successfully carried out under non-hydrocrackingconditions (i.e. lower temperature and pressure) that substantiallyreduce the hydrocracking of the feedstock material. When conditions wereincreased to much higher pressure (Example E) a product with a lowersulfur content was achieved, however some observed that there was anincrease in light hydrocarbons and wild naphtha production.

This prophetic example will provide one skilled in the art with a morespecific illustrative embodiment for conducting the processes disclosed:

Prophetic Example of DSRU Operation:

To exemplify the invention, experiments can be carried out using a firstporous sintered metal filter having a permeametric radii from 50-100micron followed by a second porous sintered metal filter having apermeametric radii from 50-0.1 micron. Examples of such filter materialsare commercially available in stainless steel and other alloy metalsfrom Mott Corp and other suppliers. Suitable membrane filters may alsobe useful. A physical entrainment filter composed of a packed bed ofparticulate material such a deactivated alumina, silica and the likewill also likely achieve the desired results. The removal of theDetrimental Solids is carried out by the physical entrainment or removalof the solids from the HMFO stream.

As part of the post Core Process treatment of the Product HMFO, thedescribed process can be carried out to condition the Product HMFO foreasier transport and handling, increased compatibility and stabilitywhen blended with other marine fuel materials (i.e. MGO or MDO), andenhance the value of these materials as low sulfur HMFO.

Table 4 contains the expected analytical test results for (A) FeedstockHMFO; (B) the Core Process Product HMFO and (C) Overall Process(Core+DSRU) from the inventive processes. These results will indicate toone of skill in the art that the production of a ULS HMFO can beachieved. It will be noted by one of skill in the art that under theconditions, the levels of hydrocarbon cracking will be minimized tolevels substantially lower than 10%, more preferably less than 5% andeven more preferably less than 1% of the total mass balance.

TABLE 4 Analytical Results A B C Sulfur Content, mass % 3.0 Less than0.5 Less than 0.1 Density @ 15° C., kg/m³ 990 950⁽¹⁾  950⁽¹⁾  KinematicViscosity @ 50° C., 380 100⁽¹⁾  100⁽¹⁾  mm²/s Pour Point, ° C. 20 10 10  Flash Point, ° C. 110 100⁽¹⁾  100⁽¹⁾  CCAI 850 820  820  AshContent, mass % 0.1   0.0   0.0 Total Sediment - Aged, 0.1   0.0   0.0mass % Micro Carbon Residue, 13.0   6.5   6.5 mass % H2S, mg/kg 0 0 0Acid Number, mg KO/g 1   0.5 Less than 0.5 Water, vol % 0.5 0 0 SpecificContaminants, mg/kg Vanadium 180 20  20  Sodium 30 1 1 Aluminum 10 1 1Silicon 30 3 3 Calcium 15 1 1 Zinc 7 1 1 Phosphorous 2 0 0 Nickle 40 5 5Iron 20 2 2 Distillation, ° C./° F. IBP 160/320  120/248 120/248  5% wt235/455  225/437 225/437 10% wt 290/554  270/518 270/518 30% wt 410/770 370/698 370/698 50% wt 540/1004 470/878 470/878 70% wt 650/1202 580/1076  580/1076 90% wt 735/1355  660/1220  660/1220 FBP 820/1508 730/1346  730/1346 C:H Ratio (ASTM D3178) 1.2   1.3   1.3 SARA AnalysisSaturates 16 22  22  Aromatics 50 50  50  Resins 28 25  25  Asphaltenes6 3 3 Asphaltenes, wt % 6.0   2.5   2.5 Total Nitrogen, mg/kg 40003000   3000   Note: ⁽¹⁾property will be adjusted to a higher value bypost process removal of light material via distillation or strippingfrom product HMFO.

One of skill in the art will know that the Aluminum and Siliconcontaminates are directly correlated to the cat fines and other mineralsolids present in the Feedstock HMFO. The primary source of these solidsis the inclusion of FCC slurry oil as a component of the Feedstock HMFO,although other sources may also contribute to these contaminations. Thelow levels of Aluminum and Silicon are achieved in the Product HMFO andone of skill in the art will appreciate this indicates a significantreduction in the cat fines and other Detrimental Solids present in theProduct HMFO. Further solids removal will be achieved with the postprocessing DSRU and it is expected that solids with a diameter in therange of 0.1 to 100 microns will be removed by the DSRU from the ProductHMFO.

It will be appreciated by those skilled in the art that changes could bemade to the illustrative embodiments described above without departingfrom the broad inventive concepts thereof. It is understood, therefore,that the inventive concepts disclosed are not limited to theillustrative embodiments or examples disclosed, but it is intended tocover modifications within the scope of the inventive concepts asdefined by the claims.

The invention claimed is:
 1. A process for reducing the EnvironmentalContaminants and Detrimental Solids in a Feedstock Heavy Marine FuelOil, the process comprising: contacting a Feedstock Heavy Marine FuelOil, wherein the Feedstock Heavy Marine Fuel Oil is compliant with ISO8217 (2017) Table 2 as a residual marine fuel, except for: theconcentration of the Environmental Contaminates is greater than 0.5 mass%, wherein the Environmental Contaminates are selected from the groupconsisting of sulfur, vanadium, nickel, iron, aluminum plus silicon andcombinations thereof; and, the presence of Detrimental Solids, whereinthe Detrimental Solids are suspended solid particulate materials in theFeedstock Heavy Marine Fuel Oil having a diameter in the range of 1000microns to 0.1 microns, with a Detrimental Solids Removal Unit to give apre-treated Feedstock Heavy Marine Fuel Oil that is substantially freeof the Detrimental Solids; mixing a quantity of the pre-treatedFeedstock Heavy Marine Fuel Oil with a quantity of an Activating Gasmixture to give a Feedstock Mixture; contacting the Feedstock Mixturewith one or more catalyst materials under reactive conditions sufficientto both: i) decrease the concentration of Environmental Contaminants toless than 0.5 mass % and ii) minimize the level of hydrocracking in theFeedstock Mixture to less than about 10% volume swell resulting fromhydrocracking, forming a Process Mixture from said Feedstock Mixturewherein said Process Mixture is composed of a Product Heavy Marine FuelOil liquid component, gaseous components and by-product hydrocarboncomponents; receiving said Process Mixture and separating a ProductHeavy Marine Fuel Oil liquid component of the Process Mixture from thegaseous components and by-product hydrocarbon components of the ProcessMixture and, discharging the Product Heavy Marine Fuel Oil liquidcomponent as a Product Heavy Marine Fuel Oil wherein the Product HeavyMarine Fuel Oil complies with ISO 8217 (2017) Table 2 as a residualmarine fuel and has a maximum Environmental Contaminants content betweenthe range of 0.01 mass % to 0.5 mass %.
 2. The process of claim 1wherein said Feedstock Heavy Marine Fuel Oil has a sulfur content (ISO14596 or ISO 8754) between the range of 5.0 mass % to 1.0 mass %.
 3. Theprocess of claim 1, wherein said Product Heavy Marine Fuel Oil has amaximum sulfur content (ISO 14596 or ISO 8754) between the range of 0.01mass % to 0.5 mass %.
 4. The process of claim 1, wherein said FeedstockHeavy Marine Fuel Oil has: a kinematic viscosity at 50° C. (ISO 3104)between the range from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO3675) between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in therange of 780 to 870; a flash point (ISO 2719) no lower than 60° C.; atotal sediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbonresidue—micro method (ISO 10370) less than 20.00 mass %.
 5. The processof claim 1, wherein the detrimental solids removal unit is a reactorvessel having one or more beds of a dense packed inert catalystmaterial.
 6. The process of claim 1, wherein the catalyst materials areselected to minimize hydrocracking under the reactive conditions and areselected from the group consisting of: a hydrodemetallization catalystcomprising one or more sulfided transition metals selected from thegroup consisting of group 6, 8, 9 and 10 of the Periodic Table supportedon an inorganic oxide carrier; a hydrotransition catalyst comprising oneor more sulfided transition metals selected from the group consisting ofgroup 6, 8, 9 and 10 of the Periodic Table supported on an inorganicoxide carrier; a hydrodesulfurization catalyst comprising one, or moresulfided transition metals selected from the group consisting of group6, 8, 9 and 10 of the Periodic Table supported on an inorganic oxidecarrier; and wherein the Activating Gas is selected from mixtures ofnitrogen, hydrogen, carbon dioxide, gaseous water, and methane, suchthat Activating Gas has an ideal gas partial pressure of hydrogen(p_(H2)) greater than 80% of the total pressure of the Activating Gasmixture (P).
 7. The process of claim 6, wherein the reactive conditions,to minimize the level of hydrocracking in the Feedstock Mixture include:a ratio of the quantity of the Activating Gas to the quantity ofFeedstock Heavy Marine Fuel Oil in the range of 250 scf gas/bbl ofFeedstock Heavy Marine Fuel Oil to 10,000 scf gas/bbl of Feedstock HeavyMarine Fuel Oil; and, a total pressure between of 250 psig and 3000psig; and, an indicated temperature between of 500 F to 900 F, and, aliquid hourly space velocity between 0.05 hr⁻¹ and 1.0 hr⁻¹.
 8. Theprocess of claim 1, wherein said Product Heavy Marine Fuel Oil has: akinematic viscosity at 50° C. (ISO 3104) between the range from 180mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675) between the range of991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; aflash point (ISO 2719) no lower than 60° C.; a total sediment—aged (ISO10307-2) less than 0.10 mass %; and a carbon residue—micro method (ISO10370) less than 20.00 mass and an aluminum plus silicon (ISO 10478)content less than 60 mg/kg.
 9. The process of claim 1 wherein theDetrimental Solids Removal Unit removes the Detrimental Solids from theFeedstock, Heavy Marine Fuel Oil by physical entrainment of theDetrimental Solids and wherein the Detrimental Solids Removal Unit iscomprised of one or ore solids removal element selected from the groupconsisting of: a porous sintered metal filter having a permeametricradii from 50 to 100 microns; a porous sintered metal filter having apermeametric radii from 50 to 0.1 microns, a packed bed of deactivatedparticulate alumina, a packed bed of deactivated silica, andcombinations thereof.
 10. A process for reducing EnvironmentalContaminates and Detrimental Solids in a Feedstock Heavy Marine FuelOil, the process comprising: mixing a quantity of Feedstock Heavy MarineFuel Oil, wherein the Feedstock Heavy Marine Fuel Oil is compliant withISO 8217 (2017) Table 2 as a residual marine fuel, except for: theconcentration of the Environmental Contaminates is greater than 0.5 mass%, wherein the Environmental Contaminates are selected from the groupconsisting of sulfur, vanadium, nickel, iron, aluminum plus silicon, andcombinations thereof; and, the presence of Detrimental Solids, whereinthe Detrimental Solids are suspended solid particulate materials in theFeedstock Heavy Marine Fuel Oil having a diameter in the range of 1000microns to 0.1 microns, with a quantity of Activating Gas mixture togive a Feedstock Mixture; substantially removing the Detrimental Solidsfrom the Feedstock Mixture and; subsequently contacting the FeedstockMixture with one or more catalyst materials under reactive conditionssufficient to both: i) decrease the concentration of EnvironmentalContaminants in the Feedstock Mixture to less than 0.5 mass % and ii)minimize the volume of hydrocracking to less than about 10% volume swellfrom hydrocracking, to form a Process Mixture from said FeedstockMixture, wherein said Process Mixture is composed of a Product HeavyMarine Fuel Oil liquid component, a by-product hydrocarbon component, abulk gaseous component, a residual Detrimental Solids component, and aresidual gas component; directly and subsequently receiving said ProcessMixture in one or more first separation vessels that are not underreactive conditions and separating the bulk gaseous components of theProcess Mixture from the remaining components of the Process Mixture;directly and subsequently receiving the remaining components of theProcess Mixture in one or more second separation vessels that are notunder reactive conditions and separating the residual gaseous componentand the by-product hydrocarbon component from the Product Heavy MarineFuel Oil liquid component and the residual Detrimental Solids componentof the Process Mixture; and subsequently passing the Product HeavyMarine Fuel Oil liquid component and the residual Detrimental Solidscomponent of the Process Mixture into a Detrimental Solids Removal Unitto remove the residual Detrimental Solids from the Product Heavy MarineFuel Oil liquid component of the Process Mixture, and, subsequentlydischarging the Product Heavy Marine Fuel Oil liquid component of theProcess Mixture as a Product Heavy Marine Fuel Oil, and the ProductHeavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2 as aresidual marine fuel and has a maximum Environmental Contaminantscontent between the range of 0.01 mass % to 0.5 mass %.
 11. The processof claim 10 wherein said Feedstock Heavy Marine Fuel Oil has a sulfurcontent (ISO 14596 or ISO 8754) between the range of 5.0 mass % to 1.0mass %.
 12. The process of claim 10, wherein said Feedstock Heavy MarineFuel Oil has a kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the rangeof 780 to 870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbonresidue—micro method (ISO 10370) less than 20.00 mass %.
 13. The processof claim 10, wherein the one or more catalyst materials are selected tominimize hydrocracking under the reactive conditions and are selectedfrom the group consisting of: a hydrodemetallization catalyst comprisingone or more sulfided transition metals selected from the groupconsisting of group 6, 8, 9 and 10 of the Periodic Table supported on aninorganic oxide carrier; a hydrotransition catalyst comprising one ormore sulfided transition metals selected from the group consisting ofgroup 6, 8, 9 and 10 of the Periodic Table supported on an inorganicoxide carrier; a hydrodesulfurization catalyst comprising one or moresulfided transition metals elected from the group consisting of group 6,8, 9 and 10 of the Periodic Table supported on an inorganic oxidecarrier; and wherein the Activating Gas is selected from mixtures ofnitrogen, hydrogen, carbon dioxide, gaseous water, and methane, suchthat Activating Gas has an ideal gas partial pressure of hydrogen(p_(H2)) greater than 80% of the total pressure of the Activating Gasmixture (P).
 14. The process of claim 13, wherein the reactiveconditions selected to minimize the level of hydrocracking in theFeedstock Mixture include: a ratio of the quantity of the Activating Gasto the quantity of Feedstock Heavy Marine Fuel Oil in the range of 250scf gas/bbl of Feedstock Heavy Marine Fuel Oil to 10,000 scf gas/bbl ofFeedstock Heavy Marine Fuel Oil; and, a total pressure between of 250psig and 3000 psig; and, an indicated temperature between of 500 F to900 F, and, a liquid hourly space velocity between 0.05 hr⁻¹ and 1.0hr⁻¹.
 15. The process of claim 10, wherein said Product Heavy MarineFuel Oil has: a of kinematic viscosity at 50° C. (ISO 3104) between therange from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the rangeof 780 to 870; a flash point (ISO 2719) no lower than 60° C.; a totalsediment—aged (ISO 10307-2) less than 0.10 mass %; and a carbonresidue—micro method (ISO 10370) less than 20.00 mass %, and a aluminumplus silicon (ISO 10478) content less than 60 mg/kg.
 16. The process ofclaim 10 wherein the Detrimental Solids Removal Unit removes theDetrimental Solids from the Product Heavy Marine Fuel Oil by physicalentrainment of the Detrimental Solids and wherein the Detrimental SolidsRemoval Unit is comprised of one ore solids removal element selectedfrom the group consisting of: a porous sintered metal filter having apermeametric radii from 50 to 100 microns; a porous sintered metalfilter having a permeametric radii from 50 to 0.1 microns, a packed bedof deactivated particulate alumina, a packed bed of deactivated silica,and combinations thereof.
 17. A process for reducing the EnvironmentalContaminants and the Detrimental Solids in a Feedstock Heavy Marine FuelOil, the process consisting of: a. contacting a Feedstock Heavy MarineFuel Oil with a Detrimental Solids Removal Unit to give a pre-treatedFeedstock Heavy Marine Fuel Oil, wherein the Feedstock Heavy Marine FuelOil is compliant with ISO 8217 (2017) Table 2 as a residual marine fuel,except: the concentration of the Environmental Contaminates is greaterthan 0.5 mass %, and wherein the Environmental Contaminates are selectedfrom the group consisting of sulfur, vanadium, nickel, iron, aluminumplus silicon, and combinations thereof; and, the Detrimental Solids arepresent, wherein the Detrimental Solids are suspended solid particulatematerials in the Feedstock Heavy Marine Fuel Oil having a diameter inthe range of 1000 microns to 0.1 microns; b. subsequently mixing aquantity of the pre-treated Feedstock Heavy Marine Fuel Oil with aquantity of an Activating Gas mixture to give a Feedstock Mixture; c.hydrodemetallization treatment of the Feedstock Mixture with one or morehydrodemetallization catalyst, materials and sending the effluent fromStep c) directly to step d); d. hydrodesulfurization treatment of theeffluent from step c with one or more hydrodesulfurization catalystmaterials; wherein the combination of steps c and d form a ProcessMixture from said Feedstock Mixture in the absence of hydrocrackingcatalyst and wherein said Process Mixture is composed of a Product HeavyMarine Fuel Oil liquid component, gaseous components and by-producthydrocarbon components and, wherein the combination of steps c and dtake place in one or more reaction vessels under reactive conditionssufficient to both: i) decrease the concentration of EnvironmentalContaminants to less than 0.5 mass % in the Product Heavy Marine FuelOil liquid component, and ii) minimize the level of hydrocracking in theProduct Heavy Marine Fuel Oil liquid component to less than about 10%volume swell attributable to hydrocracking; e. directly receiving saidProcess Mixture from step d in at least one separation vessel andseparating the Product Heavy Marine Fuel Oil liquid component of theProcess Mixture from the gaseous components and by-product hydrocarboncomponents of the Process Mixture and, f. discharging the Product HeavyMarine Fuel Oil liquid component from the at least one separation vesselas a Product Heavy Marine Fuel Oil to one or more storage vessels forthe Product Heavy Marine Fuel Oil, wherein the Product Heavy Marine FuelOil complies with ISO 8217 (2017) Table 2 as a residual marine fuel andhas a Environmental Contaminants content between the range of 0.01 mass% to 0.5 mass %.
 18. A process for reducing the sulfur and DetrimentalSolids content in a Feedstock Heavy Marine Fuel Oil, the process stepsconsisting of: a. mixing a quantity of the Feedstock Heavy Marine FuelOil with a quantity of an Activating Gas mixture to give a FeedstockMixture, wherein the Feedstock Heavy Marine Fuel Oil is compliant withISO 8217 (2017) Table 2 as a residual marine fuel, except for: theconcentration of sulfur is greater than 0.5 mass %; and, the DetrimentalSolids are present, wherein the Detrimental Solids are suspended solidparticulate materials in the Feedstock Heavy Marine Fuel Oil having adiameter in the range of 1000 microns to 0.1 microns; b. separating theDetrimental Solids from the Feedstock Mixture to form a FeedstockMixture substantially free from Detrimental Solids and subsequentlysending the Feedstock Mixture substantially free from Detrimental Solidsfrom b directly to c; c. hydrodemetallization treatment of the FeedstockMixture substantially free from Detrimental Solids with one or morehydrodemetallization catalyst materials and sending the resultingeffluent from c) directly to d); d. hydrodesulfurization treatment ofthe resulting effluent from c with one or more hydrodesulfurizationcatalyst materials and forming a Process Mixture in the absence of ahydrocracking catalyst, wherein said Process Mixture is composed of aProduct Heavy Marine Fuel Oil liquid component, gaseous components, andby-product hydrocarbon components, and wherein steps c and d take placein one or more reaction vessels under reactive conditions sufficient toboth: i) decrease the concentration of sulfur to less than 0.5 mass % inthe Product Heavy Marine Fuel Oil liquid component, and ii) minimize thelevel of hydrocracking of the Feedstock Mixture produces a less thanabout 10% volume swell attributable to hydrocracking in the ProductHeavy Marine Fuel Oil liquid component; e. directly receiving saidProcess Mixture in at least one separation vessel not under reactiveconditions and separating the Product Heavy Marine Fuel Oil liquidcomponent of the Process Mixture from the gaseous components andby-product hydrocarbon components of the Process Mixture and, f.discharging the Product Heavy Marine Fuel Oil liquid component from theat least one separation vessel as a Product Heavy Marine Fuel Oil to oneor more storage vessels for the Product Heavy Marine Fuel Oil, whereinthe Product Heavy Marine Fuel Oil complies with ISO 8217 (2017) Table 2as a residual marine fuel and has a sulfur content between the range of0.01 mass % to 0.5 mass %.